JP2018145092A - Intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass capable of suppressing generation and growth of foaming even when the laminated glass has been exposed for a long period of time under a comparatively high temperature.SOLUTION: An intermediate film 1 for laminated glass includes a first layer 2, and a second layer 3 stacked on one surface 2a of the first layer 2. Each of the first layer 2 and the second layer 3 contains a polyvinyl acetal resin and a plasticizer. When viscoelasticity of the resin film is measured using the first layer 2 as a resin film (glass transition temperature Tg (°C)) or a resin film (glass transition temperature Tg (°C)) containing 100 pts.wt. of the polyvinyl acetal resin contained in the first layer 2 and 60 pts.wt. of triethylene glycol di-2-ethylhexanoate (3GO) as the plasticizer, a ratio (G'(Tg+170)/G'(Tg+30)) of an elastic modulus G' is 0.18 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an interlayer film for laminated glass having a multilayer structure of at least two layers, and more specifically, an interlayer film for laminated glass, each layer containing a thermoplastic resin and a plasticizer, and the interlayer film for laminated glass It is related with the laminated glass using.

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates.

  As an example of the interlayer film for laminated glass, the following Patent Document 1 discloses that 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one of an alkali metal salt and an alkaline earth metal salt. A sound insulation layer containing 0.001 to 1.0 parts by weight of a metal salt of and 30 parts by weight or more of a plasticizer is disclosed. This sound insulation layer may be a single layer and used as an intermediate film.

  Furthermore, the following Patent Document 1 also describes a multilayer intermediate film in which the sound insulation layer and other layers are laminated. The other layer laminated on the sound insulation layer is composed of 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less are included.

JP 2007-070200 A

  When the laminated glass is formed using the interlayer film described in Patent Document 1, the sound insulation in the frequency region near 2000 Hz of the laminated glass is not sufficient, and therefore the sound insulation performance is inevitably lowered due to the coincidence effect. There is. In particular, the sound insulation properties at around 20 ° C. of this laminated glass may not be sufficient.

  Here, the coincidence effect means that when a sound wave is incident on the glass plate, the transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs.

  In addition, when a laminated glass is formed using a multilayer interlayer film in which the sound insulating layer described in Patent Document 1 and other layers are laminated, the sound insulating property in the vicinity of 20 ° C. of the laminated glass can be increased to some extent. it can. However, since the multilayer interlayer film has the sound insulating layer, foaming may occur in the laminated glass using the multilayer interlayer film.

  Furthermore, in recent years, in order to improve the sound insulation of the laminated glass, it has been studied to increase the content of the plasticizer in the interlayer film. When the content of the plasticizer in the interlayer film is increased, the sound insulation of the laminated glass can be improved. However, when the plasticizer content is increased, foaming may occur in the laminated glass.

  Moreover, the laminated glass used for a building or a vehicle is often used in a state exposed to sunlight, and is often exposed to a relatively high temperature for a long period of time. For example, the laminated glass may be exposed to an environment exceeding 50 ° C. When the laminated glass is exposed to a relatively high temperature for a long period of time, there is a problem that foaming and foaming are more likely to occur.

  An object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass capable of suppressing the generation of foaming and the growth of foaming even when the laminated glass is exposed to a relatively high temperature for a long period of time, and the intermediate for laminated glass It is to provide a laminated glass using a film.

  A limited object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass excellent in sound insulation, and a laminated glass using the interlayer film for laminated glass.

  According to a wide aspect of the present invention, a first layer containing a polyvinyl acetal resin and a plasticizer is laminated on one surface of the first layer, and contains a polyvinyl acetal resin and a plasticizer. When the viscoelasticity of the resin film is measured using the first layer as a resin film, the glass transition temperature of the resin film is Tg (° C.) Ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) of elastic modulus G ′ (Tg + 170) at (Tg + 170) ° C. to elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. is 0.18 or more. An interlayer film for laminated glass is provided.

  According to a wide aspect of the present invention, a first layer containing a polyvinyl acetal resin and a plasticizer is laminated on one surface of the first layer, and the polyvinyl acetal resin and the plasticizer are And 100 parts by weight of the polyvinyl acetal resin contained in the first layer, and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer. When the viscoelasticity of the resin film was measured using the resin film containing the resin film, the elastic modulus G ′ (Tg + 170) at (Tg + 170) ° C. was obtained when the glass transition temperature of the resin film was Tg (° C.). An interlayer film for laminated glass having a ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) to an elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. of 0.18 or more is provided.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more, or the polyvinyl in the first layer. It is preferable that the degree of acetylation of the acetal resin is less than 8 mol% and the degree of acetalization is 68 mol% or more. The degree of acetylation of the polyvinyl acetal resin in the first layer is preferably 8 mol% or more. Furthermore, it is also preferable that the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol% and the degree of acetalization is 68 mol% or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the first layer includes a compound having a boron atom.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the compound having a boron atom is selected from the group consisting of lithium metaborate, sodium tetraborate, potassium tetraborate, boric acid, and boric acid ester. Contains at least one selected.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the elastic modulus G ′ (Tg + 30) is 200,000 Pa or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 6.5. It is as follows.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 2. 5 to 3.2.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 50 parts by weight or more.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 55 parts by weight or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the content of hydroxyl groups in the polyvinyl acetal resin in the first layer is 30 mol% or less.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, a third layer that is laminated on the other surface of the first layer and contains a polyvinyl acetal resin and a plasticizer is further provided. It has been.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is in the second and third layers. The content of the plasticizer is more than 100 parts by weight of the polyvinyl acetal resin.

  Each of the polyvinyl acetal resins contained in the first to third layers preferably contains a polyvinyl butyral resin. The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. It is preferable to include at least one selected from the group consisting of

  The laminated glass according to the present invention comprises first and second laminated glass constituent members and an intermediate film sandwiched between the first and second laminated glass constituent members, and the intermediate film comprises: 1 is an interlayer film for laminated glass constructed according to the present invention.

  The interlayer film for laminated glass according to the present invention includes a first layer containing a polyvinyl acetal resin and a plasticizer, laminated on one surface of the first layer, and a polyvinyl acetal resin and a plasticizer. And the above ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more, so that the laminated glass using the interlayer film has a relatively high temperature. Even if it is exposed to the bottom for a long time, generation of foam and growth of foam can be suppressed.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG. FIG. 3 shows a loss tangent tan δ when the viscoelasticity of the resin film is measured using a resin film containing polyvinyl acetal resin contained in the first layer and triethylene glycol di-2-ethylhexanoate. It is a figure for demonstrating the relationship between temperature, and the relationship between elastic modulus G 'and temperature.

  Hereinafter, the present invention will be clarified by giving specific embodiments and examples of the present invention with reference to the drawings.

  In FIG. 1, the intermediate film for laminated glasses which concerns on one Embodiment of this invention is typically shown with sectional drawing.

  The intermediate film 1 shown in FIG. 1 includes a first layer 2, a second layer 3 stacked on one surface 2 a (first surface) of the first layer 2, and the other of the first layer 2. And a third layer 4 laminated on the surface 2b (second surface). The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass. The intermediate film 1 is a multilayer intermediate film.

  The first layer 2 is disposed between the second layer 3 and the third layer 4, and is sandwiched between the second layer 3 and the third layer 4. In the present embodiment, the first layer 2 is an intermediate layer, and the second and third layers 3 and 4 are surface layers. However, the second and third layers 3 and 4 are intermediate layers, and other interlayer films for laminated glass are further laminated on the outer surfaces 3a and 4a of the second and third layers 3 and 4. May be.

  Each of the first to third layers 2 to 4 preferably contains a polyvinyl acetal resin and a plasticizer.

  The main feature of this embodiment is that the resin contains 100 parts by weight of the polyvinyl acetal resin contained in the first layer 2 and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer. When the viscoelasticity of the resin film A was measured using the film A (Test Method A), the elastic modulus at (Tg + 170) ° C. when the glass transition temperature of the resin film A was Tg (° C.) The ratio of G ′ (Tg + 170) to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more.

  In this embodiment, when the first layer 2 is used as the resin film B and the viscoelasticity of the resin film B is measured (test method B), the glass transition temperature of the resin film B is Tg (° C. ), The ratio of the elastic modulus G ′ (Tg + 170) at (Tg + 170) ° C. to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. (G ′ (Tg + 170) / G ′ (Tg + 30)) It is 0.18 or more.

  In the test method B, the first layer 2 is used as the resin film B, and the first layer 2 itself is the resin film B.

  The resin film B is the first layer 2 and includes the polyvinyl acetal resin and the plasticizer in a weight ratio in the first layer 2. In the test method B, it is preferable to measure the elastic modulus G ′ (Tg + 170) and the higher elastic modulus G ′ (Tg + 30) after transferring the plasticizer in the interlayer film 1 for laminated glass. In the above test method B, the laminated glass interlayer film 1 is stored at a humidity of 30% (± 3%) and a temperature of 23 ° C. for one month, and after transferring the plasticizer in the laminated glass interlayer film 1, the elasticity It is more preferable to measure the modulus G ′ (Tg + 170) and the elastic modulus G ′ (Tg + 30).

  The glass transition temperature Tg (° C.) indicates the peak temperature of the loss tangent tan δ obtained from the measurement result obtained by measuring the viscoelasticity.

  In the interlayer film for laminated glass having a multilayer structure, the present inventors have found that a plasticizer migrates between the respective layers, and as a result, a layer having a high plasticizer content is formed. It was found that the plasticizer migrated from the first layer to the first layer, and as a result, the plasticizer content in the first layer increased. Furthermore, when a layer having a high plasticizer content is formed, that is, when the content of the plasticizer in the first layer is increased, foaming is likely to occur in the laminated glass using the interlayer film for laminated glass, and further foaming occurs. It has also been found that once foaming occurs, foaming grows with the resulting foaming as a nucleus.

  As a result of intensive studies to suppress the occurrence of foaming and the growth of foaming, the present inventors have found that the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) according to Test Method A or Test Method B is It has also been found that, by being 0.18 or more, the occurrence of foaming and the growth of foaming can be sufficiently suppressed even when the laminated glass using the interlayer film is exposed to a relatively high temperature for a long time. Even if there is much content of the plasticizer in the 1st layer 2, since generation | occurrence | production of foaming and the growth of foaming in a laminated glass can fully be suppressed, the sound-insulating property of a laminated glass can be improved. In particular, the second and third layers 3 and 4 are laminated on both surfaces of the first layer 2 configured so that the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more. Further, by using the interlayer film 1 for laminated glass, even if the laminated glass using the interlayer film is exposed to a relatively high temperature for a long time, generation of foam and growth of foam can be further suppressed.

  The ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more, preferably 0.2 or more, and preferably 1.0 or less. When the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is not less than the above lower limit and not more than the above upper limit, even if the laminated glass is stored for a long period of time under fairly severe conditions, Generation and growth of foaming can be more effectively suppressed.

  Moreover, the laminated glass used for a building or a vehicle is often used in a state exposed to sunlight, and is often exposed to a relatively high temperature. For example, the laminated glass may be exposed to an environment exceeding 50 ° C. The ratio in the test method A (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more, or the ratio in the test method B (G ′ (Tg + 170) / G ′ (Tg + 30)). If the laminated glass is 0.18 or more, even if the laminated glass is stored for a long period of time at a very severe high temperature (for example, 40 to 60 ° C., sometimes exceeding 50 ° C.), the occurrence of foaming and the growth of the foaming in the laminated glass Can be further suppressed.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass at a high temperature, the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is preferably 0.2 or more, more preferably It is 0.22 or more, more preferably 0.3 or more, particularly preferably 0.4 or more, more preferably 0.95 or less. In particular, when the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is controlled by the average degree of polymerization of the polyvinyl alcohol resin, or when it is controlled by a compound having a boron atom, the occurrence of foaming and foaming in the laminated glass The above ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is preferably 0.22 or more, more preferably 0.8 because the growth can be sufficiently suppressed and the sound insulation of the laminated glass can be further enhanced. 3 or more, more preferably 0.4 or more, preferably 0.9 or less, more preferably 0.88 or less. Further, when the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.85 or less, the intermediate film can be easily formed.

  Using the resin film A containing 100 parts by weight of the polyvinyl acetal resin contained in the first layer 2 and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, the resin film When the viscoelasticity of A is measured (test method A), when the glass transition temperature of the resin film A is Tg (° C.), the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. (Tg + 30) The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) to the elastic modulus G ′ (Tg + 30) at ° C. is preferably 0.65 or more.

  When the first layer 2 is used as the resin film B and the viscoelasticity of the resin film B is measured (test method B), when the glass transition temperature of the resin film B is Tg (° C.) The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. is 0.65 or more. Preferably there is.

  When the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more The occurrence of foaming and the growth of foaming in laminated glass can be further suppressed over a wide temperature range. When the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.20 or more and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more Further, the occurrence of foaming and the growth of foaming in the laminated glass can be further suppressed over a wide temperature range. However, the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) in Test Method A is 0.18 or more, or the ratio in Test Method B (G ′ (Tg + 170) / G ′ (Tg + 30). )) Is 0.18 or more, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) in Test Method A may be less than 0.65, and the ratio in Test Method B ( G ′ (Tg + 80) / G ′ (Tg + 30)) may be less than 0.65.

  The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is preferably 1.0 or less. When the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more, it is easy to more effectively suppress generation of foam and growth of foam in the laminated glass. Further, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is not less than the above lower limit and not more than the above upper limit, it is easy to more effectively suppress generation of foam and growth of foam in the laminated glass. It is.

  From the viewpoint of further suppressing the generation of foaming and the growth of foaming in the laminated glass, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.7 or more, and more preferably 0.95. It is below, More preferably, it is 0.75 or more, More preferably, it is 0.9 or less. In particular, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is controlled by the average degree of polymerization of the polyvinyl alcohol resin, the occurrence of foaming and the growth of foam in the laminated glass are sufficiently suppressed, and Since the sound insulation can be further improved, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is preferably 0.65 or more, more preferably 0.66 or more, and further preferably 0.67 or more. Particularly preferably, it is 0.7 or more, preferably 0.82 or less, more preferably 0.8 or less. Further, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.82 or less, or 0.8 or less, the intermediate film can be easily formed.

  As a method of setting the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) according to the test method A or the test method B to 0.18 or more, when synthesizing the polyvinyl acetal resin in the first layer 2 In addition, a method of using a polyvinyl alcohol resin having a relatively high average degree of polymerization, a method of strengthening the interaction between the molecules of the polyvinyl acetal resin in the first layer 2, and a boron atom in the first layer 2 The method of adding the compound which has is mentioned. Examples of a method for strengthening the interaction between the molecules of the polyvinyl acetal resin in the first layer 2 include a method for physically crosslinking the molecules of the polyvinyl acetal resin and a method for chemically crosslinking the molecules. Especially, since the intermediate film 1 can be easily formed by an extruder, a method of using a polyvinyl alcohol resin having a relatively high average degree of polymerization when synthesizing the polyvinyl acetal resin in the first layer 2. A method of physically cross-linking the molecules of the polyvinyl acetal resin in the first layer 2 and a method of adding a compound having a boron atom to the first layer 2 are preferable.

  As a method of setting the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B to 0.65 or more, when synthesizing the polyvinyl acetal resin in the first layer 2 Examples thereof include a method using a polyvinyl alcohol resin having a relatively high average degree of polymerization and a method for strengthening the interaction between molecules of the polyvinyl acetal resin in the first layer 2. Examples of a method for strengthening the interaction between the molecules of the polyvinyl acetal resin in the first layer 2 include a method for physically crosslinking the molecules of the polyvinyl acetal resin and a method for chemically crosslinking the molecules. Especially, since the intermediate film 1 can be easily formed by an extruder, a method of using a polyvinyl alcohol resin having a relatively high average degree of polymerization when synthesizing the polyvinyl acetal resin in the first layer 2. Alternatively, a method of physically cross-linking the molecules of the polyvinyl acetal resin in the first layer 2 is preferable.

  An example of the relationship between the loss tangent tan δ obtained by the viscoelasticity measurement and the temperature and the relationship between the elastic modulus G ′ and the temperature will be described with reference to FIG.

  The loss tangent tan δ and the temperature have a relationship as shown in FIG. The temperature at the peak P of the loss tangent tan δ is the glass transition temperature Tg.

  Further, the glass transition temperature Tg at the elastic modulus G ′ of the broken line A2 shown in FIG. 3 and the glass transition temperature Tg at the elastic modulus G ′ of the solid line A1 are the same temperature. For example, the smaller the amount of change D of the elastic modulus G ′ (Tg + 170) with respect to the elastic modulus G ′ (Tg + 30), the smaller the amount of matching, the higher the temperature (for example, 40 to 60 ° C., in some cases exceeding 50 ° C.). Generation | occurrence | production of foaming in glass and the growth of foaming can be suppressed effectively. The change amount D1 in the elastic modulus G ′ of the solid line A1 is smaller than the change amount D2 in the elastic modulus G ′ of the broken line A2. Therefore, in FIG. 3, the case where the change D1 shows the elastic modulus G ′ of the solid line A1 where the change D1 is relatively small is considerably severer than the case where the change D1 shows the elastic modulus G ′ of the solid line A1. Occurrence of foaming and growth of foaming in laminated glass at a high temperature can be effectively suppressed.

  Further, the glass transition temperature Tg at the elastic modulus G ′ of the broken line A2 shown in FIG. 3 and the glass transition temperature Tg at the elastic modulus G ′ of the solid line A1 are the same temperature. For example, in the laminated glass under normal temperature (for example, 10 to 20 ° C.) to high temperature (for example, 30 to 50 ° C.), the smaller the change amount D of the elastic modulus G ′ (Tg + 80) is based on the elastic modulus G ′ (Tg + 30). Generation of foam and growth of foam can be effectively suppressed. The change amount D3 in the elastic modulus G 'of the solid line A1 is smaller than the change amount D4 in the elastic modulus G' of the broken line A2. Therefore, in FIG. 3, the case where the change amount D3 indicates the elastic modulus G ′ of the solid line A1 where the change amount D3 indicates the relatively small elastic line G1 is higher than the case where the change amount D3 indicates the elastic modulus G ′ of the relatively large broken line A2. Generation of foam and growth of foam in the laminated glass at a high temperature can be effectively suppressed.

  The G ′ (Tg + 30) is preferably 200,000 Pa or more. G ′ (Tg + 30) is more preferably 220,000 Pa or more, further preferably 230,000 Pa or more, particularly preferably 240,000 Pa or more, preferably 10 million Pa or less, more preferably 5 million Pa or less, particularly preferably It is 1,000,000 Pa or less, most preferably 500,000 Pa or less, and most preferably 300,000 Pa or less. Generation | occurrence | production of foaming and growth of foaming in a laminated glass can be suppressed more effectively as said G '(Tg + 30) is more than the said minimum.

  The relationship between the elastic modulus G ′ and the temperature is greatly influenced by the kind of the polyvinyl acetal resin, particularly greatly influenced by the average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin. It is not greatly affected by the type, and the content of the general plasticizer is not greatly affected by the content of the plasticizer. The above ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) when a plasticizer such as a monobasic organic acid ester other than 3GO is used as the plasticizer, in particular triethylene glycol di- The above ratio when using 2-ethylbutyrate (3GH) and triethylene glycol di-n-heptanoate (3G7) (G ′ (Tg + 170) / G ′ (Tg + 30)) is the above ratio when using 3GO. This is not significantly different from (G ′ (Tg + 170) / G ′ (Tg + 30)). Further, when the content of the plasticizer is 50 to 80 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin, the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) does not greatly differ. The above ratio (G ′ (Tg + 170) / G ′) measured using a resin film containing 100 parts by weight of a polyvinyl acetal resin and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer. (Tg + 30)) is not significantly different from the above ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) measured using the first layer 2 itself. This is also true for the above ratio (G ′ (Tg + 80) / G ′ (Tg + 30)).

  Both of the above ratios (G ′ (Tg + 170) / G ′ (Tg + 30)) obtained by the above test method A and the above test method B are preferably 0.18 or more. The ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is more preferably 0.18 or more. Both of the above ratios (G ′ (Tg + 80) / G ′ (Tg + 30)) obtained by the above test method A and the above test method B are preferably 0.65 or more. The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.65 or more. The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) in Test Method A may be less than 0.65, and the ratio in Test Method B (G ′ (Tg + 80) / G ′ (Tg + 30)). ) May be less than 0.65. Both the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) in Test Method A and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) in Test Method B are less than 0.65. There may be.

  Moreover, when the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is 50 parts by weight or more, the sound insulation of the laminated glass can be sufficiently enhanced.

  Hereinafter, the detail of each component contained in the said 1st-3rd layer of an intermediate film is demonstrated.

(Polyvinyl acetal resin)
When the first to third layers each contain a polyvinyl acetal resin and a plasticizer, the adhesive strength of the first to third layers can be increased. For this reason, the adhesive force of the intermediate film with respect to the laminated glass constituent member can be further increased. The polyvinyl acetal resin may be a polyvinyl acetal resin not modified with a carboxylic acid, or a polyvinyl acetal resin modified with a carboxylic acid (a carboxylic acid-modified polyvinyl acetal resin). In the present specification, the “polyvinyl acetal resin” includes a polyvinyl acetal resin not modified with a carboxylic acid and a carboxylic acid-modified polyvinyl acetal resin.

  The polyvinyl acetal resin can be produced by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin. The carboxylic acid-modified polyvinyl acetal resin is obtained by acetalizing a carboxylic acid-modified polyvinyl alcohol resin with an aldehyde.

  From the viewpoint of enhancing the dispersibility of the compound having a boron atom or further suppressing the generation of foaming and the growth of foaming in the laminated glass, the compound has the boron atom when acetalizing the polyvinyl alcohol resin. It is preferable to add a compound.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass, the polyvinyl acetal resin in the first layer is obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of 1500 or more. It is preferable. From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass, the polyvinyl acetal resin in the first layer is obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. It is also preferable.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass, the preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resin used to obtain the polyvinyl acetal resin in the first layer is 1600, and more. A preferred lower limit is 1700, a more preferred lower limit is 1800, a particularly preferred lower limit is 1900, a most preferred lower limit is 2000, a preferred upper limit is 7000, a preferred upper limit is 6000, a preferred upper limit is 5000, a preferred upper limit is 4900, and a preferred upper limit is 4500. Further, in order to further suppress the occurrence of foaming and the growth of foaming in the laminated glass, the preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin in the first layer is 3010, A more preferred lower limit is 3050, a still more preferred lower limit is 3500, a still more preferred lower limit is 3600, a particularly preferred lower limit is 4000, and a most preferred lower limit is 4050. In particular, the occurrence of foaming and the growth of foaming in the laminated glass are further suppressed, the sound insulation of the laminated glass is sufficiently enhanced, and the interlayer film can be easily molded, so that the polyvinyl acetal resin in the first layer is obtained. The average degree of polymerization of the polyvinyl alcohol resin used for the above is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, or 3800 or less. More preferably, it is more preferably 3600 or less, and most preferably 3500 or less.

  According to the test method A and the test method B, the average polymerization degree of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin in the first layer is not less than the lower limit. It is easy to make the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) satisfy the lower limit and the upper limit, and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is the above. It has also been found that it is easy to satisfy the lower limit and the upper limit.

  In the present invention, the first layer may contain only a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree exceeding 3000 as a polyvinyl acetal resin, and the average polymerization degree is 3000. A polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin exceeding the above range and other polyvinyl acetal resins may be contained. When the other polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree of 3000 or less (hereinafter also referred to as “polyvinyl acetal resin Z”), the average polymerization degree is 3000. Polyvinyl acetal obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in a total of 100% by weight of the polyvinyl acetal resin and the polyvinyl acetal resin Z obtained by acetalizing a polyvinyl alcohol resin exceeding The preferred lower limit of the resin content is 5% by weight, the more preferred lower limit is 50% by weight, the still more preferred lower limit is 70% by weight, the particularly preferred lower limit is 90% by weight, the preferred upper limit is 100% by weight, and the more preferred upper limit is 95% by weight. In . In particular, since the occurrence of foaming and the growth of foaming in laminated glass can be further suppressed, the other polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. It is preferable.

  The average degree of polymerization of the polyvinyl alcohol resin is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.

  The polyvinyl acetal resin in the second and third layers can be produced by acetalizing a polyvinyl alcohol resin. The preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resin for obtaining the polyvinyl acetal resin in the second and third layers is 200, the more preferred lower limit is 500, the still more preferred lower limit is 1000, the particularly preferred lower limit is 1500, the preferred upper limit. Is 4000, more preferred upper limit is 3,500, further preferred upper limit is 3000, and particularly preferred upper limit is 2500. When the average degree of polymerization satisfies the preferable lower limit, the penetration resistance of the laminated glass can be further enhanced. When the average degree of polymerization satisfies the preferable upper limit, the intermediate film can be easily formed. The second and third layers may contain the carboxylic acid-modified polyvinyl acetal resin.

  The average degree of polymerization of the polyvinyl alcohol resin used to obtain the polyvinyl acetal resin in the first layer is greater than the average degree of polymerization of the polyvinyl alcohol resin used to obtain the polyvinyl acetal resin in the second and third layers. Is preferably high, preferably 500 or higher, more preferably 800 or higher, more preferably 1000 or higher, still more preferably 1300 or higher, and particularly preferably 1800 or higher.

  The polyvinyl alcohol resin can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol resin is generally in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and in the range of 80 to 99.8 mol%. More preferably.

  The aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among these, n-butyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, and n-butyraldehyde is more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

  The polyvinyl acetal resin is preferably a polyvinyl butyral resin. Each of the polyvinyl acetal resins contained in the first to third layers preferably contains a polyvinyl butyral resin. Synthesis of polyvinyl butyral resin is easy. Furthermore, the use of the polyvinyl butyral resin allows the intermediate film to have a more appropriate adhesive force with respect to the laminated glass component. Furthermore, light resistance, weather resistance, etc. can be further improved.

  The preferred lower limit of the hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin contained in the first layer as the intermediate layer is 16 mol%, more preferred lower limit is 18 mol%, and still more preferred lower limit is 20 mol%. A particularly preferred lower limit is 22 mol%, a preferred upper limit is 30 mol%, a more preferred upper limit is 29 mol%, a still more preferred upper limit is 27 mol%, and a particularly preferred upper limit is 25 mol%. When the hydroxyl group content satisfies the preferable lower limit, the adhesive strength of the first layer can be further increased. When the hydroxyl group content satisfies the preferable upper limit, the sound insulating properties of the laminated glass can be further enhanced. Furthermore, the flexibility of the intermediate film is increased, and the handleability of the intermediate film can be further enhanced.

  In addition, when the content rate of the hydroxyl group of polyvinyl acetal resin is low, the hydrophilic property of polyvinyl acetal resin will become low. For this reason, content of a plasticizer can be increased and as a result, the sound insulation of a laminated glass can be made still higher. When the hydroxyl group content of the polyvinyl acetal resin in the first layer is lower than the hydroxyl group content of the polyvinyl acetal resin in the second and third layers, the plasticity of the first layer is The content of the agent can be increased. Since the sound insulation of the laminated glass can be further enhanced, the hydroxyl group content of the polyvinyl acetal resin in the first layer is determined by the hydroxyl groups of the polyvinyl acetal resin in the second and third layers. The content is preferably 2 mol% or less, more preferably 4 mol% or less, still more preferably 6 mol% or less, and particularly preferably 8 mol% or less.

  The preferred lower limit of the hydroxyl group content of the polyvinyl acetal resin contained in the second and third layers as the surface layer is 26 mol%, more preferred lower limit is 27 mol%, and still more preferred lower limit is 28 mol%, A particularly preferred lower limit is 29 mol%, a most preferred lower limit is 30 mol%, a preferred upper limit is 35 mol%, a more preferred upper limit is 34 mol%, a still more preferred upper limit is 33 mol%, a particularly preferred upper limit is 32 mol%, and a most preferred upper limit. Is 31.5 mol%. When the hydroxyl group content satisfies the preferable lower limit, the adhesive strength of the intermediate film can be further increased. When the hydroxyl group content satisfies the preferable upper limit, the flexibility of the intermediate film is increased, and the handleability of the intermediate film can be further enhanced.

  The content of hydroxyl groups in the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%). . The amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of the polyvinyl acetal resin is bonded by a method based on JIS K6728 “Testing method for polyvinyl butyral”. it can.

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin contained in the first layer is preferably 30 mol% or less. When the degree of acetylation exceeds 30 mol%, the reaction efficiency in producing a polyvinyl acetal resin may be reduced.

  The preferable lower limit of the degree of acetylation of the polyvinyl acetal resin contained in the first layer is 0.1 mol%, the more preferable lower limit is 0.5 mol%, the still more preferable lower limit is 0.8 mol%, and the preferable upper limit. Is 24 mol%, a more preferred upper limit is 20 mol%, a still more preferred upper limit is 19.5 mol%, and a particularly preferred upper limit is 15 mol%. The preferable lower limit of the degree of acetylation of the polyvinyl acetal resin contained in the second and third layers is 0.1 mol%, the more preferable lower limit is 0.5 mol%, and the still more preferable lower limit is 0.8 mol%. The preferred upper limit is 20 mol%, the more preferred upper limit is 5 mol%, the still more preferred upper limit is 2 mol%, and the particularly preferred upper limit is 1.5 mol%. When the acetylation degree satisfies the preferable lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced. When the acetylation degree satisfies the preferable upper limit, the moisture resistance of the intermediate film can be further enhanced. Since the sound insulation of the laminated glass can be further enhanced, the degree of acetalization of the polyvinyl acetal resin in the first layer is different from the degree of acetalization of the polyvinyl acetal resin in the second and third layers. The acetylation degree of the polyvinyl acetal resin in the first layer is 3 mol% or more higher than the acetylation degree of the polyvinyl acetal resin in the second and third layers. Preferably, it is more preferably at least 5 mol%, more preferably at least 7 mol%, particularly preferably at least 10 mol%.

  The degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, This is a value expressed as a percentage (mol%) of the mole fraction obtained by dividing by. The amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

  The preferred lower limit of the degree of acetalization of the polyvinyl acetal resin contained in the first layer is 50 mol%, more preferred lower limit is 54 mol%, still more preferred lower limit is 58 mol%, and particularly preferred lower limit is 60 mol%, preferably The upper limit is 85 mol%, the more preferable upper limit is 80 mol%, and the more preferable upper limit is 79 mol%. The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin contained in the second and third layers is 60 mol%, the more preferable lower limit is 65 mol%, the still more preferable lower limit is 66 mol%, and the particularly preferable lower limit is 67 mol%. %, A preferred upper limit is 75 mol%, a more preferred upper limit is 72 mol%, a still more preferred upper limit is 71 mol%, and a particularly preferred upper limit is 70 mol%. When the degree of acetalization satisfies the preferable lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced. When the said acetalization degree satisfy | fills the said preferable upper limit, reaction time required in order to manufacture polyvinyl acetal resin can be shortened. Since the sound insulation of the laminated glass can be further enhanced, the degree of acetylation of the polyvinyl acetal resin in the first layer and the degree of acetylation of the polyvinyl acetal resin in the second and third layers. When the absolute value of the difference between the first and second layers is 3 or less, the degree of acetalization of the polyvinyl acetal resin in the first layer is greater than the degree of acetalization of the polyvinyl acetal resin in the second and third layers. Is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, and particularly preferably 10 mol% or more.

  The degree of acetalization is a value obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, and expressed as a percentage (mol%).

  The degree of acetalization was determined by measuring the amount of acetyl groups and the amount of vinyl alcohol (hydroxyl content) by a method based on JIS K6728 “Testing methods for polyvinyl butyral”, and calculating the mole fraction from the obtained measurement results. Then, it can be calculated by subtracting the amount of acetyl groups and the amount of vinyl alcohol from 100 mol%.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the degree of acetylation are measured by a method according to JIS K6728 “Testing methods for polyvinyl butyral” or ASTM D1396-92. Can be calculated from the results. Measurement by a method according to ASTM D1396-92 is preferred.

  Furthermore, since the occurrence of foaming and the growth of foaming in the laminated glass can be further suppressed, and the sound insulation of the laminated glass can be further enhanced, the polyvinyl acetal resin contained in the first layer is Polyvinyl acetal resin (hereinafter also referred to as “polyvinyl acetal resin A”) having an acetylation degree of less than 8 mol%, or a polyvinyl acetal resin (hereinafter referred to as “polyvinyl acetal resin B”) having an acetylation degree of 8 mol% or more. It is also preferred that

  The degree of acetylation a of the polyvinyl acetal resin A is less than 8 mol%, preferably 7.5 mol% or less, preferably 7 mol% or less, and preferably 6 mol% or less, 5 mol% or less is preferable, 0.1 mol% or more is preferable, 0.5 mol% or more is preferable, 0.8 mol% or more is preferable, and 1 mol% or more is preferable. Preferably, it is 2 mol% or more, preferably 3 mol% or more, and preferably 4 mol% or more. When the acetylation degree a is not more than the above upper limit and not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced, and the sound insulation of the laminated glass can be further enhanced.

  A preferable lower limit of the degree of acetalization a of the polyvinyl acetal resin A is 68 mol%, a more preferable lower limit is 70 mol%, a further preferable lower limit is 71 mol%, a particularly preferable lower limit is 72 mol%, and a preferable upper limit is 85 mol%. A preferred upper limit is 83 mol%, a more preferred upper limit is 81 mol%, and a particularly preferred upper limit is 79 mol%. When the acetalization degree a is not less than the above lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetalization degree a is not more than the above upper limit, the reaction time necessary for producing the polyvinyl acetal resin A can be shortened.

  The hydroxyl group content a of the polyvinyl acetal resin A is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 24 mol% or less, preferably 23 mol% or less, preferably 16 mol% or more, and 18 mol% or more. It is preferable that it is 19 mol% or more, and it is preferable that it is 20 mol% or more. When the hydroxyl group content a is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced. When the hydroxyl group content a is equal to or higher than the lower limit, the adhesive strength of the intermediate film can be further increased.

  The polyvinyl acetal resin A is preferably a polyvinyl butyral resin.

  The degree of acetylation b of the polyvinyl acetal resin B is 8 mol% or more, preferably 9 mol% or more, preferably 10 mol% or more, preferably 11 mol% or more, 12 It is preferably at least mol%, preferably at most 30 mol%, preferably at most 28 mol%, preferably at most 26 mol%, preferably at most 24 mol%, It is preferably at most 1 mol%, more preferably at most 19.5 mol%. When the acetylation degree b is not less than the above lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetylation degree b is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin B can be shortened. Especially, since reaction time required in order to manufacture polyvinyl acetal resin B can be shortened further, it is preferable that the acetylation degree b of the said polyvinyl acetal resin B is less than 20 mol%.

  The preferable lower limit of the degree of acetalization b of the polyvinyl acetal resin B is 50 mol%, the more preferable lower limit is 52.5 mol%, the still more preferable lower limit is 54 mol%, the particularly preferable lower limit is 60 mol%, and the preferable upper limit is 80 mol%. A more preferred upper limit is 77 mol%, a still more preferred upper limit is 74 mol%, and a particularly preferred upper limit is 71 mol%. When the acetalization degree b is equal to or higher than the lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetalization degree b is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin B can be shortened.

  The hydroxyl content b of the polyvinyl acetal resin B is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 18 mol% or more, preferably 20 mol% or more, preferably 22 mol% or more, and 23 mol% or more. It is preferable. When the hydroxyl group content b is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced. When the hydroxyl group content b is not less than the above lower limit, the adhesive strength of the intermediate film can be further increased.

  The polyvinyl acetal resin B is preferably a polyvinyl butyral resin.

  The polyvinyl acetal resin A and the polyvinyl acetal resin B are preferably obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree of 1500 or more with an aldehyde. The aldehyde is preferably an aldehyde having 1 to 10 carbon atoms, and more preferably an aldehyde having 4 or 5 carbon atoms. The preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resins A and B is 1600, the preferred lower limit is 1700, the preferred lower limit is 1800, the preferred lower limit is 1900, the preferred lower limit is 2000, the preferred lower limit is 2100, the preferred upper limit is 7000, and the preferred upper limit is 6000, a preferred upper limit is 5000, a preferred upper limit is 4900, and a preferred upper limit is 4500. The polyvinyl acetal resin in the first layer is particularly preferably obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of more than 3000 and less than 4000.

  The molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is generally 1.1 or more, preferably 1.2 or more, more preferably 2 As mentioned above, Preferably it is 6.7 or less, More preferably, it is 6.5 or less, More preferably, it is 3.4 or less.

  The preferred lower limit of the molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is 1.2, the more preferred lower limit is 1.5, the still more preferred lower limit is 2.0, and the particularly preferred lower limit is 2.5. The preferred upper limit is 5.5, the more preferred upper limit is 5, the still more preferred upper limit is 4.6, and the particularly preferred upper limit is 3.2. The molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is particularly preferably 2.5 to 3.2. The molecular weight distribution ratio indicates the ratio of the weight average molecular weight Mw of the polyvinyl acetal resin contained in the first layer to the number average molecular weight Mn of the polyvinyl acetal resin contained in the first layer. When the molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is equal to or higher than the lower limit and equal to or lower than the upper limit, or 2.5 to 3.2. The ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B satisfy the lower limit and the upper limit. It has also been found that it is easy to do so, and further, generation of foaming and growth of foaming in the laminated glass can be further effectively suppressed. Among them, the occurrence of foaming and the growth of foaming in the laminated glass can be further effectively suppressed, and the sound insulation of the laminated glass can be further enhanced, so that the polyvinyl acetal resin contained in the first layer is used. Preferably, the plasticizer content is 50 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin contained in the first layer. In particular, when the polyvinyl acetal resin contained in the first layer contains the polyvinyl acetal resin B, the molecular weight distribution ratio of the polyvinyl acetal resin B is 6.5 or less, and the first layer It is preferable that content of the said plasticizer with respect to 100 weight part of said polyvinyl acetal resins contained in is 55 weight part or more.

  In addition, the said weight average molecular weight and the said number average molecular weight show the weight average molecular weight and number average molecular weight in polystyrene conversion by a gel permeation chromatography (GPC) measurement. For example, in order to measure a weight average molecular weight and a number average molecular weight in terms of polystyrene, GPC measurement of a polystyrene standard sample having a known molecular weight is performed. As polystyrene standard samples (“Shodex Standard SM-105”, “Shodex Standard SH-75” manufactured by Showa Denko KK), weight average molecular weights 580, 1,260, 2,960, 5,000, 10,100, 21,000 , 28,500, 76,600, 196,000, 630,000, 11,130,000, 2,190,000, 3,150,000, 3,900,000. An approximate straight line obtained by plotting the molecular weight against the elution time indicated by the peak top of each standard sample peak is used as a calibration curve. From the multilayer intermediate film left in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for one month, the surface layer (the second and third layers) and the intermediate layer (the first layer) And the peeled first layer (intermediate layer) is dissolved in tetrahydrofuran (THF) to prepare a 0.1 wt% solution. The obtained solution can be analyzed by a GPC apparatus, and a weight average molecular weight and a number average molecular weight can be measured. As a GPC apparatus, a GPC apparatus (Hitachi High-Tech "RI: L2490, auto sampler: L-2200, pump: L-2130, GPC apparatus to which a GPC light scattering detector (" Model 270 (RALS + VISCO) "manufactured by VISCOTEK)) is connected. Column oven: L-2350, column: series of GL-A120-S and GL-A100MX-S ”), the weight average molecular weight and the number average molecular weight can be analyzed.

  Moreover, from the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass and obtaining a laminated glass excellent in sound insulation, the polyvinyl acetal resin contained in the first layer is modified with carboxylic acid. A polyvinyl acetal resin is preferable, and a carboxylic acid-modified polyvinyl butyral resin is more preferable. By using a carboxylic acid-modified polyvinyl acetal resin, it is easy to make the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) according to Test Method A or Test Method B satisfy the lower limit and the upper limit. And it is easy for the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B to satisfy the lower limit and the upper limit. The present inventors have found that the use of a carboxylic acid-modified polyvinyl acetal resin can more effectively suppress the occurrence of foaming and the growth of foam in laminated glass.

  The carboxylic acid-modified polyvinyl acetal resin has an ethylene group having an acetal group, an ethylene group having an acetyl group, an ethylene group having a hydroxyl group, and an ethylene group modified with a carboxylic acid. Examples of the carboxylic acid include unsaturated dicarboxylic acids and unsaturated tricarboxylic acids. The carboxylic acid is preferably an unsaturated dicarboxylic acid such as maleic acid or itaconic acid. The ratio of the ethylene group having the acetal group, the ethylene group having the acetyl group, the ethylene group having the hydroxyl group, and the ethylene structural unit modified with the carboxylic acid is not particularly limited. In the case of mol%, the proportion of the ethylene structural unit modified with the carboxylic acid is more than 0 mol%, preferably 10 mol% or less, preferably 9 mol% or less, preferably 8 mol% or less. It is preferably 7 mol% or less, preferably 6 mol% or less, preferably 5 mol% or less, preferably 4 mol% or less, preferably 3 mol% or less. Preferably, it is 2 mol% or less, and preferably 1 mol% or less.

(Plasticizer)
The plasticizer contained in each of the first to third layers is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphate plasticizers such as organic phosphate plasticizers and organic phosphorous acid plasticizers. It is done. Of these, organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

  The monobasic organic acid ester is not particularly limited. For example, a glycol ester obtained by reaction of glycol with a monobasic organic acid, and triethylene glycol or tripropylene glycol with a monobasic organic acid. Examples include esters. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.

  The polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.

  The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di 2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, alkyd oil-modified sebacic acid, and a mixture of phosphate ester and adipate. Organic ester plasticizers other than these may be used. Other adipic acid esters other than the above-mentioned adipic acid esters may be used.

  The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  The plasticizer is preferably a diester plasticizer represented by the following formula (1). By using this diester plasticizer, the sound insulation of the laminated glass can be further enhanced.

  In said formula (1), R1 and R2 respectively represent a C5-C10 organic group, R3 represents an ethylene group, an isopropylene group, or n-propylene group, p represents the integer of 3-10. . R1 and R2 in the above formula (1) are each preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer is selected from the group consisting of triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-n-heptanoate (3G7). It is preferable to include at least one selected from the group consisting of triethylene glycol di-2-ethylhexanoate. The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. It is preferable to include at least one selected from the group consisting of By using these preferable plasticizers, the sound insulation of the laminated glass can be further enhanced.

  The content of the plasticizer in each layer of the interlayer film is not particularly limited.

  From the viewpoint of sufficiently increasing the sound insulation of the laminated glass, the plasticizer content in 100 parts by weight of the polyvinyl acetal resin in the first layer is preferably 40 parts by weight or more. By configuring the first layer so that the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) is 0.18 or more even if the plasticizer content of the first layer is large. The occurrence of foaming and the growth of foaming in laminated glass can be suppressed.

  The preferred lower limit of the plasticizer content relative to 100 parts by weight of the polyvinyl acetal resin in the first layer is 40 parts by weight, more preferred lower limit is 45 parts by weight, still more preferred lower limit is 50 parts by weight, and particularly preferred lower limit is 55 parts by weight. The most preferred lower limit is 60 parts by weight, the preferred upper limit is 80 parts by weight, the more preferred upper limit is 78 parts by weight, the still more preferred upper limit is 75 parts by weight, and the particularly preferred upper limit is 70 parts by weight. Further, the preferred lower limit of the plasticizer content relative to 100 parts by weight of the polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in the first layer is 40 parts by weight. A preferred lower limit is 45 parts by weight, a more preferred lower limit is 50 parts by weight, a particularly preferred lower limit is 55 parts by weight, a most preferred lower limit is 60 parts by weight, a preferred upper limit is 80 parts by weight, a more preferred upper limit is 78 parts by weight, and a more preferred upper limit is 75 parts by weight, and a particularly preferred upper limit is 70 parts by weight. When content of the said plasticizer satisfy | fills the said preferable minimum, the penetration resistance of a laminated glass can be improved further. As the content of the plasticizer in the first layer is larger, the sound insulation of the laminated glass can be further enhanced. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further.

  The preferred lower limit of the plasticizer content relative to 100 parts by weight of the polyvinyl acetal resin in the second and third layers is 25 parts by weight, the more preferred lower limit is 30 parts by weight, the still more preferred lower limit is 35 parts by weight, and the preferred upper limit is 50 parts. More preferred upper limit is 45 parts by weight, still more preferred upper limit is 40 parts by weight, and particularly preferred upper limit is 39 parts by weight. When content of the said plasticizer satisfy | fills the said preferable minimum, the adhesive force of an intermediate film will become high and the penetration resistance of a laminated glass can be improved further. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further.

  From the viewpoint of further improving the sound insulation of the laminated glass, the plasticizer content in 100 parts by weight of the polyvinyl acetal resin in the first layer is 100 parts by weight of the polyvinyl acetal resin in the second and third layers. It is preferable that there are more than each content of the plasticizer with respect to. From the viewpoint of further improving the sound insulation of the laminated glass, the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin in the first layer is 100 parts by weight of the polyvinyl acetal resin in the second and third layers. It is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 12 parts by weight or more, and particularly preferably 15 parts by weight or more.

(Compound having boron atom)
From the viewpoint of further suppressing generation of foaming and growth of foaming in the laminated glass and obtaining a laminated glass excellent in sound insulation, the first layer preferably contains a compound having a boron atom. Although the compound which has the said boron atom is not specifically limited, A metaborate, tetraborate, boric acid, boric acid ester, etc. are mentioned. From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass and obtaining a laminated glass excellent in sound insulation, the compound having a boron atom is metaborate, tetraborate, borate, Boric acid or a boric acid ester is preferable.

  Examples of the metaborate include lithium metaborate. Examples of the tetraborate include sodium tetraborate and potassium tetraborate. Examples of the boric acid ester include n-butyl boronic acid, n-hexyl boronic acid, tri-n-octyl borate, trioctadecyl boronic acid, 2-isopropyl-4,4,5,5-tetramethyl-1,3, Examples include 2-dioctaborolane, triisopropyl borate, tri-n-propyl borate, and tri-n-butyl borate.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in laminated glass and obtaining a laminated glass excellent in sound insulation, the compound having a boron atom is lithium metaborate, sodium tetraborate, potassium tetraborate. Boric acid, n-butylboronic acid, n-hexylboronic acid, tri-n-octylborate, trioctadecylboronic acid, 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioctaborolane And at least one selected from the group consisting of triisopropyl borate, tri-n-propyl borate, and tri-n-butyl borate. From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in laminated glass and obtaining a laminated glass excellent in sound insulation, the compound having a boron atom is lithium metaborate, sodium tetraborate, potassium tetraborate. And at least one selected from the group consisting of boric acid.

  Although the molecular weight of the said compound which has a boron atom is not specifically limited, Preferably it is 1000 or less, More preferably, it is 500 or less.

  The compound having a boron atom is preferably added to the resin. As a method of adding the compound having a boron atom to a resin, a method in which a solution in which the compound having a boron atom is dissolved in a solvent is added to the resin at the time of acetalization reaction when obtaining a polyvinyl acetal resin, And a method in which a compound having a boron atom is mixed with a solvent or a surfactant and added to a resin. The compound having a boron atom may be added to a resin for obtaining a polyvinyl acetal resin, or may be added to a polyvinyl acetal resin. As for the compound having a boron atom, the compound having the boron atom may be directly added to the resin, or a solution in which the compound having the boron atom is dissolved in a solvent may be added to the resin. A mixture of a compound having an atom and a solvent or a surfactant may be added to the resin. By using the solvent or the surfactant, the compound having a boron atom can be more uniformly dispersed in the resin. Further, by uniformly dispersing the compound having a boron atom in the resin, extrusion molding of each layer in the intermediate film becomes easy.

  Examples of the solvent include pure water, alcohol, plasticizer, polyalkylene polyol, polyalkylene glycol alkyl ether, and polyalkylene glycol aryl ether. For example, the polyalkylene polyol is preferably tetraethylene glycol, the polyalkylene glycol alkyl ether is preferably tetraethylene glycol phenyl ether, and the polyalkylene glycol aryl ether is preferably polyalkylene glycol phenyl ether.

  Examples of the surfactant include polyalkylene glycol alkyl ether and polyalkylene glycol aryl ether. For example, the polyalkylene glycol alkyl ether is preferably polyethylene glycol alkyl ether, and the polyalkylene glycol aryl ether is preferably polyethylene glycol phenyl ether. Especially, since the compound which has a boron atom in resin can be disperse | distributed more uniformly, polyalkylene glycol alkyl ether or polyalkylene glycol aryl ether is preferable.

  The preferred lower limit of the surfactant content relative to 100 parts by weight of the polyvinyl acetal resin in the first layer is 0.1 parts by weight, the more preferred lower limit is 1 part by weight, the still more preferred lower limit is 5 parts by weight, and the particularly preferred lower limit. Is 10 parts by weight, a preferred upper limit is 50 parts by weight, a more preferred upper limit is 40 parts by weight, a further preferred upper limit is 30 parts by weight, a particularly preferred upper limit is 20 parts by weight, and a most preferred upper limit is 15 parts by weight. If content of the said surfactant satisfy | fills the said preferable minimum, the compound which has a boron atom in resin can be disperse | distributed more uniformly. When content of the said surfactant satisfy | fills the said preferable upper limit, the penetration resistance of a laminated glass can be improved further.

  The preferable lower limit of the total of the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer and the content of the surfactant with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 45 parts by weight, more preferred lower limit is 50 parts by weight, still more preferred lower limit is 55 parts by weight, particularly preferred lower limit is 60 parts by weight, preferred upper limit is 85 parts by weight, more preferred upper limit is 80 parts by weight, and still more preferred upper limit is 75 parts by weight. A particularly preferred upper limit is 70 parts by weight. If the said total satisfy | fills the said preferable minimum, the sound insulation of a laminated glass can be improved further. When the total satisfies the preferable upper limit, the penetration resistance of the laminated glass can be further enhanced.

  A preferable lower limit of the content of the compound having a boron atom with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 0.01 part by weight, a more preferable lower limit is 0.05 part by weight, and a still more preferable lower limit is 0.1 part by weight. Part by weight, the preferred upper limit is 5 parts by weight, the more preferred upper limit is 1 part by weight, and the more preferred upper limit is 0.5 part by weight. When the content of the boron atom-containing compound satisfies the preferable lower limit, the generation of foam and the growth of foam in the laminated glass can be further suppressed. When the content of the boron atom-containing compound satisfies the preferable upper limit, the transparency of the laminated glass can be further increased.

  The preferred lower limit of the content of boron atoms in the first layer is 1 ppm, the preferred lower limit is 2 ppm, the preferred lower limit is 5 ppm, the preferred lower limit is 10 ppm, the preferred lower limit is 15 ppm, the preferred lower limit is 20 ppm, and the preferred upper limit is 10,000 ppm, The preferred upper limit is 5000 ppm, the preferred upper limit is 3000 ppm, the preferred upper limit is 1000 ppm, the preferred upper limit is 900 ppm, the preferred upper limit is 800 ppm, the preferred upper limit is 700 ppm, the preferred upper limit is 600 ppm, the preferred upper limit is 500 ppm, the preferred upper limit is 400 ppm, the preferred upper limit is 300 ppm, A preferable upper limit is 200 ppm, a preferable upper limit is 100 ppm, and a preferable upper limit is 50 ppm. When the content of the boron atom satisfies the preferable lower limit, generation of foam and growth of foam in the laminated glass can be further suppressed. When the boron atom content satisfies the preferable upper limit, the interlayer film for laminated glass can be easily molded. The boron atom in the first layer includes not only a boron atom derived from the compound having the boron atom but also a boron atom contained in the interlayer film for laminated glass according to the present invention. The boron atom content in the first layer can be measured by ICP emission spectroscopic analysis.

(Other ingredients)
Each of the first to third layers is, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescent whitening. An additive such as an agent and an infrared absorber may be contained.

(Method for producing interlayer film for laminated glass and laminated glass)
Although it does not specifically limit as a manufacturing method of the intermediate film for laminated glasses which concerns on this invention, After forming the said 1st-3rd layer, respectively using the resin composition containing the said polyvinyl acetal resin and the said plasticizer. For example, a method of laminating the second layer, the first layer, and the third layer in this order, and coextruding the resin composition using an extruder, For example, a method of laminating a layer, the first layer, and the third layer in this order may be used. Since the production efficiency of the interlayer film is excellent, it is preferable that the second and third layers contain the same polyvinyl acetal resin, and the second and third layers contain the same polyvinyl acetal resin and More preferably, the same plasticizer is contained, and the second and third layers are more preferably formed of the same resin composition.

  From the viewpoint of enhancing the dispersibility of the compound having a boron atom and further suppressing the generation of foaming and the growth of foaming in the laminated glass, the composition for obtaining the first layer contains the boron atom. It is preferable that the compound which has is included.

  Each of the interlayer films for laminated glass according to the present invention is used to obtain a laminated glass.

  FIG. 2 is a cross-sectional view schematically showing an example of a laminated glass using the intermediate film 1 shown in FIG.

  A laminated glass 11 shown in FIG. 2 includes a first laminated glass constituting member 12, a second laminated glass constituting member 13, and the intermediate film 1. The intermediate film 1 is sandwiched between the first and second laminated glass constituent members 12 and 13.

  The first laminated glass constituting member 12 is laminated on the outer surface 3 a of the second layer 3. The second laminated glass component 13 is laminated on the outer surface 4 a of the third layer 4. Accordingly, the laminated glass 11 is composed of the first laminated glass constituting member 12, the second layer 3, the first layer 2, the third layer 4, and the second laminated glass constituting member 13 in this order. It is laminated and configured.

  Examples of the first and second laminated glass constituent members include glass plates and PET (polyethylene terephthalate) films. Laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like. Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, netted plate glass, and lined plate glass. The organic glass is a synthetic resin glass substituted for inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  From the viewpoint of further improving the penetration resistance of the laminated glass, the preferable lower limit of the thickness of the interlayer film is 0.05 mm, the more preferable lower limit is 0.25 mm, the preferable upper limit is 3 mm, and the more preferable upper limit is 1.5 mm. When the thickness of the interlayer film satisfies the preferable lower limit and the preferable upper limit, the penetration resistance and transparency of the laminated glass can be further enhanced. The preferred lower limit of the thickness of the first layer is 0.01 mm, the more preferred lower limit is 0.04 mm, the still more preferred lower limit is 0.07 mm, the preferred upper limit is 0.3 mm, the more preferred upper limit is 0.2 mm, and the more preferred upper limit is 0.18 mm, and a particularly preferred upper limit is 0.16 mm. When the thickness of the first layer satisfies the above lower limit, the sound insulating property of the laminated glass can be further increased, and when the upper limit is satisfied, the transparency of the laminated glass can be further increased. A preferable lower limit of the thickness of the second and third layers is 0.1 mm, a more preferable lower limit is 0.2 mm, a still more preferable lower limit is 0.25 mm, a particularly preferable lower limit is 0.3 mm, and a preferable upper limit is 0.6 mm. A preferred upper limit is 0.5 mm, a more preferred upper limit is 0.45 mm, and a particularly preferred upper limit is 0.4 mm. When the thicknesses of the second and third layers satisfy the above lower limit, the penetration resistance of the laminated glass can be further increased, and when the upper limit is satisfied, the transparency of the laminated glass can be further increased. The ratio of the thickness of the first layer to the thickness of the intermediate film ((thickness of the first layer) / (thickness of the intermediate film)) is small, and the plasticizer contained in the first layer is contained. The larger the amount, the more foaming occurs in the laminated glass and the foam tends to grow. In particular, when the ratio in the intermediate film is 0.05 to 0.35 and the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 55 parts by weight or more, Generation | occurrence | production of foaming and the growth of foaming in the laminated glass using the intermediate film for laminated glass which concerns on invention can fully be suppressed, and the sound-insulating property of laminated glass can be improved further. The preferable lower limit of the ratio ((the thickness of the first layer) / (the thickness of the intermediate film)) is 0.06, the more preferable lower limit is 0.07, the still more preferable lower limit is 0.08, and the particularly preferable lower limit is 0.00. 1. A preferred upper limit is 0.3, a more preferred upper limit is 0.25, a still more preferred upper limit is 0.2, and a particularly preferred upper limit is 0.15.

  The thickness of the first and second laminated glass constituting members is preferably 0.5 mm or more, more preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. Moreover, when the said laminated glass structural member is a glass plate, it is preferable that the thickness of this glass plate exists in the range of 1-3 mm. When the laminated glass component is a PET film, the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.

  The manufacturing method of the said laminated glass is not specifically limited. For example, the intermediate film is sandwiched between the first and second laminated glass constituent members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, and the first and second laminated glass The air remaining between the glass component and the intermediate film is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, the laminated glass can be obtained.

  The laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes. The laminated glass is preferably laminated glass for buildings or vehicles, and more preferably laminated glass for vehicles. Laminated glass can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

  In Examples and Comparative Examples, the following polyvinyl butyral resin (polyvinyl acetal resin) was used. The degree of butyralization (degree of acetalization), the degree of acetylation and the hydroxyl group content of the polyvinyl butyral resin were measured by a method based on ASTM D1396-92. In addition, also when measured by JIS K6728 “Testing method for polyvinyl butyral”, the same numerical values as the method based on ASTM D1396-92 were shown.

Example 1
(1) Production of multilayer interlayer film Polyvinyl butyral resin obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 2310 with n-butyraldehyde (hydroxyl group content 23.4 mol%, acetylation degree 12 2 mol%, butyralization degree 64.4 mol%) 100 parts by weight, plasticizer 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) and sodium tetraborate 0.12 parts by weight And kneaded sufficiently with a mixing roll to obtain a resin composition for an intermediate layer.

  Furthermore, polyvinyl butyral resin obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 1700 with n-butyraldehyde (hydroxyl group content 30.9 mol%, acetylation degree 0.8 mol%, butyral) 37.5 parts by weight of a plasticizer, triethylene glycol di-2-ethylhexanoate (3GO), was added to 100 parts by weight of the plasticizer, and the surface layer was sufficiently kneaded with a mixing roll. A resin composition was obtained.

  By using the obtained resin composition for intermediate layer and resin composition for surface layer and coextruding with an extruder, a surface layer (thickness 350 μm), an intermediate layer (thickness 100 μm), and a surface layer (thickness 350 μm) Were produced in order.

(2) Preparation of laminated glass used for penetration resistance test The obtained multilayer interlayer film was cut into a size of 30 cm in length and 30 cm in width. Next, a multilayer intermediate film was sandwiched between two transparent float glasses (length 30 cm × width 30 cm × thickness 2.5 mm) to obtain a laminate. This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed. Crimped. The pre-pressed laminate was pressed for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass used for the penetration resistance test.

(3) Production of laminated glass used for sound insulation measurement Multilayer interlayer film is cut into a size of 30 cm in length x 2.5 cm in width, and transparent float glass (length 30 cm x width 2.5 cm x thickness 2.5 mm) is obtained. A laminated glass used for sound insulation measurement was obtained in the same manner as the laminated glass used for the penetration resistance test except that it was used.

(4) Preparation of laminated glass used for foaming test (Laminated glass used for foaming test of Test Method A)
The obtained multilayer intermediate film was cut into a size of 30 cm (length) × 15 cm (width), and stored in an environment at a temperature of 23 ° C. for 10 hours. In addition, embossing was formed on both surfaces of the obtained multilayer intermediate film, and the ten-point average roughness of the embossing was 30 μm. In the cut multilayer intermediate film, an intersection 4 between a position 8 cm inward in the vertical direction from the end of the multilayer intermediate film and a position 5 cm inward in the lateral direction from the end of the multilayer intermediate film. A through-hole having a diameter of 6 mm was formed at a location to obtain a multilayer intermediate film having a through-hole.

  A multilayer intermediate film having a through hole was sandwiched between two transparent float glasses (length 30 cm × width 15 cm × thickness 2.5 mm) to obtain a laminate. The outer peripheral edge of the laminate was sealed with a width of 2 cm from the end by heat sealing, thereby enclosing the air remaining in the emboss and the air remaining in the through hole. The laminated body was pressure-bonded at 135 ° C. and a pressure of 1.2 MPa for 20 minutes, so that the remaining air was dissolved in the multilayer interlayer film to obtain a laminated glass used for the foaming test.

(Laminated glass used for foaming test of test method B)
A laminated glass used for the foaming test of Test Method B was obtained in the same manner as the laminated glass used for the foaming test of Test Method A, except that no through-hole was formed in the multilayer interlayer film.

(Laminated glass used for foaming test of test method C)
The laminated glass used for the foaming test of Test Method C was obtained in the same manner as the laminated glass used for the foaming test of Test Method A.

(Examples 2 to 4 and Comparative Examples 1 to 4)
The composition of the first to third layers and the average degree of polymerization of the polyvinyl alcohol resin or carboxylic acid modified polyvinyl alcohol resin used to obtain the polyvinyl acetal resin or carboxylic acid modified polyvinyl acetal resin used in the first layer are shown in the following table. An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the changes were made as shown in FIG.

  In Example 4, instead of the polyvinyl butyral resin in the intermediate layer resin composition, a carboxylic acid-modified polyvinyl butyral resin (average polymerization degree 1800, hydroxyl group content 21.3 mol%, acetylation degree 12.6 mol) %, Butyralization degree 64.9 mol%, carboxylic acid modification ratio 1.2 mol%), and the composition of the first to third layers was changed as shown in Table 1 below. In the same manner as in Example 1, an interlayer film and a laminated glass were produced. Moreover, the polyvinyl butyral resin contained in the resin composition for surface layers of Examples 2 to 4 and Comparative Examples 1 to 4 was obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of 1700.

(Example 5)
In a mixed liquid in which 10 parts by weight of polyethylene glycol alkyl ether (Sanyo Chemical Co., Ltd. “Sannonic SS-70”) as surfactant A and 0.0125 parts by weight of lithium metaborate as a compound having a boron atom were mixed Then, 50 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was added and mixed well to prepare a plasticizer dispersion. Polyvinyl butyral resin obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 2300 with n-butyraldehyde (hydroxyl group content 23 mol%, acetylation degree 12.5 mol%, butyralization degree 64. The total amount of the plasticizer dispersion was added to 100 parts by weight of 5 mol%) and sufficiently kneaded with a mixing roll to obtain an intermediate layer resin composition.

  Furthermore, polyvinyl butyral resin obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 1700 with n-butyraldehyde (hydroxyl group content 30.4 mol%, acetylation degree 0.8 mol%, butyral) 38.5 parts by weight of a plasticizer, triethylene glycol di-2-ethylhexanoate (3GO) is added to 100 parts by weight of the plasticizer (68.8 mol%), and the surface layer is thoroughly kneaded with a mixing roll. A resin composition was obtained.

  By using the obtained resin composition for intermediate layer and resin composition for surface layer and coextruding with an extruder, a surface layer (thickness 350 μm), an intermediate layer (thickness 100 μm), and a surface layer (thickness 350 μm) Were produced in order.

  In the same manner as in Example 1, a laminated glass used for a penetration resistance test, a laminated glass used for sound insulation measurement, and a laminated glass used for a foaming test were produced. In addition, the foaming test was done by the test method C.

(Examples 6 to 57 and Comparative Examples 5 to 6)
Composition of plasticizer dispersion, composition of first to third layers, and average degree of polymerization, butyralization degree, and acetylation of polyvinyl alcohol resin used to obtain polyvinyl acetal resin used for first to third layers An interlayer film and a laminated glass were produced in the same manner as in Example 5 except that the degree and the hydroxyl group content were changed as shown in Tables 2 to 7 below.

  Surfactant A is polyethylene glycol alkyl ether (“SANNONIC SS-70” manufactured by Sanyo Chemical Industries), and surfactant B is polyethylene glycol alkyl ether (“NAROACTY CL-40” manufactured by Sanyo Chemical Industries, Ltd.), and surfactant C. Is polyethylene glycol phenyl ether (Daiichi Kogyo Seiyaku Co., Ltd.).

(Evaluation)
(1) Sound insulation The laminated glass is vibrated with a vibration generator for vibration testing ("Vibrator G21-005D" manufactured by KENKEN Co., Ltd.), and the vibration characteristics obtained therefrom are mechanical impedance measuring device (manufactured by RION Co., Ltd.). The vibration spectrum was analyzed with an FFT spectrum analyzer ("FFT analyzer HP3582A" manufactured by Yokogawa Hured Packard).

  From the ratio of the loss factor thus obtained and the resonance frequency of the laminated glass, a graph showing the relationship between the sound frequency (Hz) and the sound transmission loss (dB) at 20 ° C. is created. The minimum sound transmission loss (TL value) in the vicinity of 000 Hz was determined. The higher the TL value, the higher the sound insulation. The case where the TL value was 35 dB or more was determined as “◯”, and the case where the TL value was less than 35 dB was determined as “x”.

(2) Foamed state (Test Method A and Test Method B)
Five laminated glasses used for the foaming test were prepared for each multilayer interlayer film and left in an oven at 50 ° C. for 100 hours. In the laminated glass after standing, the presence or absence of foaming and the size of foaming were visually observed in a plan view (Test Method A). Further, five laminated glasses used for the foam test were prepared for each multilayer intermediate film, and left in an oven at 50 ° C. for 30 days. In the laminated glass after being left, the presence or absence of foaming and the size of foaming were visually observed in plan view (Test Method B). From the observation results, the state of foaming was determined according to the following criteria.

[Criteria for foaming state]
Foam generated in five laminated glasses was approximated by an ellipse, and the area of the ellipse was defined as the foamed area. The average value of the elliptical areas observed in the five laminated glasses was determined, and the ratio (percentage) of the average value (foamed area) of the elliptical area to the area (30 cm × 15 cm) of the laminated glass was determined.

◯: No foaming was observed in all the 5 laminated glasses. ○: The ratio of the average value of the elliptical area (foamed area) was less than 5%. △: The ratio of the average value of the elliptical area (foamed area) It was 5% or more and less than 10% x: The ratio of the average value (foaming area) of the elliptical area was 10% or more

(3) Foamed state (Test Method C)
Five laminated glasses used for the foam test were prepared for each multilayer intermediate film, and left in an oven at 60 ° C. for 50 hours. In the laminated glass after being left, the presence or absence of foaming and the size of foaming were visually observed in plan view (Test Method C). From the observation results, the state of foaming was determined according to the following criteria.

[Criteria for foaming state]
Foam generated in five laminated glasses was approximated by an ellipse, and the area of the ellipse was defined as the foamed area. The average value of the elliptical areas observed in the five laminated glasses was determined, and the ratio (percentage) of the average value (foamed area) of the elliptical area to the area (30 cm × 15 cm) of the laminated glass was determined.

◯: Foaming was not observed in all five laminated glasses. ○: The ratio of the average value of the elliptical area (foaming area) was less than 3%. △: The ratio of the average value of the elliptical area (foaming area) was It was 3% or more and less than 5%. X: The ratio of the average value (foaming area) of the elliptical area was 5% or more.

(4) Penetration resistance The laminated glass (length 30 cm x width 30 cm) used in the penetration resistance test was adjusted so that the surface temperature was 23 ° C. Next, in accordance with JIS R3212, a rigid sphere having a mass of 2260 g and a diameter of 82 mm was dropped from the height of 4 m onto the center portion of the laminated glass for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. If the number of laminated glasses in which the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was 3 or less, it was rejected. In the case of four sheets, the penetration resistance of six new laminated glasses was evaluated. In the case of 5 sheets, one additional laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. In the same manner, from a height of 5 m and 6 m, a rigid sphere having a mass of 2260 g and a diameter of 82 mm was dropped on the laminated glass of 6 sheets, and the penetration resistance of the laminated glass was evaluated. .

(5) Measurement of elastic modulus G ′ by test method A 100 parts by weight of each polyvinyl acetal resin (polyvinyl acetal resin used for the first layer) contained in the first layer of the interlayer film for laminated glass of Examples and Comparative Examples And 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer were sufficiently kneaded to obtain a kneaded product. The obtained kneaded material was press-molded with a press molding machine to obtain a resin film A having an average thickness of 0.35 mm. The obtained resin film A was allowed to stand for 2 hours at 25 ° C. and a relative humidity of 30%. After standing for 2 hours, viscoelasticity was measured using ARES-G2 manufactured by TAINSTRUMENTS. As a jig, a parallel plate having a diameter of 8 mm was used. The measurement was performed under the condition of decreasing the temperature from 100 ° C. to −10 ° C. at a temperature decrease rate of 3 ° C./min, and under the conditions of frequency 1 Hz and strain 1%. In the obtained measurement results, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). Further, from the obtained measurement result and the glass transition temperature Tg, the value of the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C., the value of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C., ( Tg + 170) The value of the elastic modulus G ′ (Tg + 170) at a temperature was read. Further, the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) were determined. For Examples 5 to 20 and Comparative Examples 5 and 6, only the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) was calculated.

(6) Measurement of Elastic Modulus G ′ by Test Method B The interlayer films for laminated glass of Examples and Comparative Examples were stored in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 1 month. Immediately after storage for 1 month, the intermediate layer was taken out by peeling the surface layer, intermediate layer and surface layer. 1 g of the peeled intermediate layer is placed in a formwork (length 2 cm × width 2 cm × thickness 0.76 mm) placed between two polyethylene terephthalate (PET) films, the temperature is 150 ° C., and the press pressure is 0 kg / cm. ² for 10 minutes and then press-molded at 80 kg / cm ² for 15 minutes. The press-molded intermediate layer was placed in a hand press set in advance at 20 ° C. and cooled by pressing at 10 MPa for 10 minutes. Next, after peeling off one PET film from a mold placed between two PET films and storing it in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 24 hours Viscoelasticity was measured using ARES-G2 manufactured by TAINSTRUMENTS. As a jig, a parallel plate having a diameter of 8 mm was used. The measurement was performed under the condition of decreasing the temperature from 100 ° C. to −10 ° C. at a temperature decrease rate of 3 ° C./min, and under the conditions of frequency 1 Hz and strain 1%. In the obtained measurement results, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). Further, from the obtained measurement result and the glass transition temperature Tg, the value of the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C., the value of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C., ( Tg + 170) The value of the elastic modulus G ′ (Tg + 170) at a temperature was read. Further, the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) were determined. For Examples 5 to 20 and Comparative Examples 5 and 6, only the ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) was calculated.

  The results are shown in Tables 1 to 7 below. In the following Tables 1-7, 3GO which is a kind of plasticizer represents triethylene glycol di-2-ethylhexanoate, and 3G7 represents triethylene glycol di-n-heptanoate. The values of the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin or carboxylic acid-modified polyvinyl acetal resin used for the first layer are also shown in Table 1 below. The number average molecular weight Mn of the polyvinyl acetal resin X used for the first layer was in the range of 50,000 to 500,000. The number average molecular weight indicates the number average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

  As shown in the above table, in the interlayer films for laminated glass of Examples and Comparative Examples, the polyvinyl acetal resin constituting the first layer and the plasticizer constituting the first layer are included in the contents shown in Table 1 above. As a result of measuring the elastic modulus G ′ of the resin film B (first layer) after transferring the plasticizer between the layers of the multilayer intermediate film using the resin film B (first layer), the resin The ratio of the film B (G ′ (Tg + 170) / G ′ (Tg + 30)) is the ratio of the resin film A containing 100 parts by weight of the polyvinyl acetal resin contained in the first layer and 60 parts by weight of 3GO (G ′ ( Tg + 170) / G ′ (Tg + 30)). Further, in the interlayer films for laminated glass of Examples and Comparative Examples, a resin film B (first film) containing the polyvinyl acetal resin constituting the first layer and the plasticizer constituting the first layer in the contents shown in Table 1 above. 1), the plasticizer was transferred between the layers of the multilayer interlayer film, and then the elastic modulus G ′ of the resin film B (first layer) was measured. As a result, the ratio of the resin film B ( G ′ (Tg + 80) / G ′ (Tg + 30)) is a ratio (G ′ (Tg + 80) / G ′) of resin film A containing 100 parts by weight of polyvinyl acetal resin and 60 parts by weight of 3GO contained in the first layer. (Tg + 30)).

DESCRIPTION OF SYMBOLS 1 ... Intermediate film 2 ... 1st layer 2a ... One side 2b ... The other side 3 ... 2nd layer 3a ... Outer surface 4 ... 3rd layer 4a ... Outer surface 11 ... Laminated glass 12 ... 1st Laminated glass constituent member 13 ... Second laminated glass constituent member

Claims (17)

A first layer containing a polyvinyl acetal resin and a plasticizer;
A second layer that is laminated on one side of the first layer and contains a polyvinyl acetal resin and a plasticizer;
When the viscoelasticity of the resin film was measured using the first layer as a resin film, the elastic modulus G at (Tg + 170) ° C. when the glass transition temperature of the resin film was Tg (° C.) The interlayer film for laminated glass having a ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) to elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. of “(Tg + 170)” is 0.18 or more. A first layer containing a polyvinyl acetal resin and a plasticizer;
A second layer that is laminated on one side of the first layer and contains a polyvinyl acetal resin and a plasticizer;
Using a resin film containing 100 parts by weight of the polyvinyl acetal resin contained in the first layer and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, When measuring the viscoelasticity, when the glass transition temperature of the resin film is Tg (° C.), the elastic modulus G ′ at (Tg + 30) ° C. of the elastic modulus G ′ (Tg + 170) at (Tg + 170) ° C. The interlayer film for laminated glass having a ratio (G ′ (Tg + 170) / G ′ (Tg + 30)) to Tg + 30) of 0.18 or more.   The degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more, or the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol%, and the acetal The interlayer film for laminated glass according to claim 1 or 2, wherein the degree of conversion is 68 mol% or more.   The interlayer film for laminated glass according to claim 3, wherein the degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more.   The interlayer film for laminated glass according to claim 3, wherein the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol%, and the degree of acetalization is 68 mol% or more.   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the first layer contains a compound having a boron atom.   The compound according to claim 6, wherein the compound having a boron atom includes at least one selected from the group consisting of lithium metaborate, sodium tetraborate, potassium tetraborate, and boric acid and a borate ester. Intermediate film for glass.   The interlayer film for laminated glass according to any one of claims 1 to 7, wherein the elastic modulus G '(Tg + 30) is 200,000 Pa or more.   The molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 6.5 or less, according to any one of claims 1 to 8. An interlayer film for laminated glass.   The intermediate for laminated glass according to claim 9, wherein a molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin included in the first layer is 2.5 to 3.2. film.   The interlayer film for laminated glass according to any one of claims 1 to 10, wherein a content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 50 parts by weight or more.   The interlayer film for laminated glass according to claim 11, wherein a content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 55 parts by weight or more.   The interlayer film for laminated glass according to any one of claims 1 to 12, wherein a content ratio of a hydroxyl group of the polyvinyl acetal resin in the first layer is 30 mol% or less.   The laminated glass according to any one of claims 1 to 13, further comprising a third layer that is laminated on the other surface of the first layer and contains a polyvinyl acetal resin and a plasticizer. Interlayer film.   Content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is more than each content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the second and third layers. The interlayer film for laminated glass according to claim 14, wherein the interlayer film is large. Each of the polyvinyl acetal resins contained in the first to third layers contains a polyvinyl butyral resin,
The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. The interlayer film for laminated glass according to claim 14 or 15, comprising at least one selected from the group consisting of: First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
Laminated glass, wherein the interlayer film is the interlayer film for laminated glass according to any one of claims 1 to 16.

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